原子Pt催化多相抗马氏C- n形成:Pt 1 δ+ -activated C=C攻击Pt 1 0激活N-H( Atomic Pt Catalyzed Heterogeneous anti-Markovnikov C-N For-mation: Pt 1 0 activating N-H for Pt 1 δ+ -activated C=C attack )

X Ma Z An H Song X Shu J He

C–N formation is of greatsignificance to synthetic chemistry,as N-containing products are widely used in chemistry, medicine, andbiology. Addition of an amine to an unsaturated carbon–carbonbond is a simple yet effective route to produce new C–N bonds.But how to effectively conduct an anti-Markovnikov addition with highselectivity has been a great challenge. Here, we proposed a strategyfor highly regioselective C–N addition via hydroamination byusing supported Pt. It has been identified that atomic-scale Pt isthe active site for C–N addition with Pt₁²⁺ for Markovnikov C–N formation and atomic Pt (Pt₁^δ+ and Pt₁⁰) contributingto anti-Markovnikov C–N formation. A selectivity of up to 92%to the anti-Markovnikov product has been achieved with atomic Pt inthe addition of styrene and pyrrolidine. A cooperating catalysis forthe anti-Markovnikov C–N formation between Pt₁^δ+ and Pt₁⁰ has been revealed.The reaction mechanism has been studied by EPR spectra and in situFT-IR spectra of adsorption/desorption of styrene and/or pyrrolidine.It has been demonstrated that Pt₁⁰ activatesamine to be electrophilic, while Pt₁^δ+ activates CC by π-bonding to make β-C nucleophilic.The attack of nucleophilic β-C to electrophilic amine affordsthe anti-Markovnikov addition. This strategy proves highly effectiveto a variety of substrates in anti-Markovnikov C–N formation,including aromatic/aliphatic amines reacting with aromatic olefins,aromatic/aliphatic olefins with aromatic amines, and linear aliphaticolefins with secondary aliphatic amines. It is believed that the resultsprovide evidence for the function of varied chemical states in monatomiccatalysis.

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